CN114388831B - Alkaline zinc-manganese battery - Google Patents
Alkaline zinc-manganese battery Download PDFInfo
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- CN114388831B CN114388831B CN202111446211.4A CN202111446211A CN114388831B CN 114388831 B CN114388831 B CN 114388831B CN 202111446211 A CN202111446211 A CN 202111446211A CN 114388831 B CN114388831 B CN 114388831B
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- battery
- manganese dioxide
- positive electrode
- alkaline zinc
- delithiated
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims description 19
- 239000000654 additive Substances 0.000 claims abstract description 52
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 17
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims description 44
- 230000001590 oxidative effect Effects 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 25
- 229910052744 lithium Inorganic materials 0.000 description 25
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an alkaline zinc-manganese dioxide battery, which comprises a shell, wherein a battery anode and a battery cathode are arranged in the shell and are separated by a diaphragm, and electrolyte is filled in the shell. The formula of the positive electrode material of the battery positive electrode is as follows: manganese dioxide accounting for 40-80 percent of the mass, a delithiated additive accounting for 10-50 percent of the mass, delithiated degree of the delithiated additive being 0.17-0.99, electrolyte accounting for 2-5 percent of the mass, a conductive agent accounting for 3-7 percent of the mass, and an adhesive accounting for 0.1-0.4 percent of the mass. According to the alkaline zinc-manganese dioxide battery, the open voltage and the voltage platform of the battery can be improved, and the battery has good discharge performance, and can simultaneously realize high-current discharge and low-current discharge.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an alkaline zinc-manganese battery.
Background
Along with the progress of the science and technology and the improvement of the living standard of people, the demands of people on various instruments and meters, medical equipment, small digital appliances, electric toys and other electrical appliances are greatly increased, and meanwhile, various miniaturized and high-tech electrical appliances, especially digital electronic equipment and devices, have higher requirements on the high-current discharge performance of the alkaline zinc-manganese battery, but the technical field of the alkaline battery has difficult realization of excellent high-current performance and excellent low-current performance.
Accordingly, there is a need for an alkaline zinc-manganese cell that at least partially addresses the above problems.
Disclosure of Invention
In the summary, a series of concepts in a simplified form are introduced, which will be further described in detail in the detailed description. The summary of the invention is not intended to define the key features and essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
In order to solve the above problems at least in part, the present invention provides an alkaline zinc-manganese dioxide battery comprising a housing in which a battery positive electrode and a battery negative electrode are disposed, the battery positive electrode and the battery negative electrode being separated by a separator, the housing being filled with an electrolyte,
the formula of the positive electrode material of the battery positive electrode is as follows:
manganese dioxide with the mass ratio of 40-80%,
the weight ratio of the delithiated additive is 10-50%, the delithiated degree of the delithiated additive is 0.17-0.99, preferably 0.32-0.96, more preferably 0.54-0.95,
the mass ratio of the positive electrolyte is 2-5%,
the mass ratio of the conductive agent is 3-7%,
the mass ratio of the adhesive is 0.1-0.4%.
According to the alkaline zinc-manganese dioxide battery, the open voltage and the voltage platform of the battery can be improved, and the battery has good discharge performance, and can simultaneously realize high-current discharge and low-current discharge.
Further, the formula of the positive electrode material is as follows:
manganese dioxide with the mass ratio of 60-73%,
the lithium-removing additive accounts for 20 to 30 percent of the mass,
the mass ratio of the positive electrolyte is 2.5-3.5%,
the conductive agent accounts for 4 to 6 percent of the mass,
the mass ratio of the adhesive is 0.3-0.4%.
Further, the method comprises the steps of,
the electrolyte and the positive electrode electrolyte are aqueous solutions of alkali metal hydroxide with mass fraction of 30-36%; and/or
The conductive agent is at least one of graphite, semi-expanded graphite, fully-expanded graphite and graphene.
Further, the delithiated state additive is made by the steps of:
fully mixing an oxidant and a ternary positive electrode material in water and heating the mixture to perform an oxidation reaction, and continuously presetting time;
and a post-treatment step, namely cleaning, filtering and drying the obtained oxidation reaction product to obtain the delithiated additive. According to the configuration, the operation is simple and convenient, the control is easy, the equipment requirement is low, the mass production cost is easy to realize, and the yield of the product is high
Further, the mass ratio of the oxidant to the ternary positive electrode material is 1:3-4:1.
Further, the oxidant is at least one selected from sodium hypochlorite, potassium hypochlorite, sodium persulfate and potassium persulfate, and the oxidant is an aqueous solution with a mass concentration of 0.05 g/mL-0.25 g/mL. The oxidant of the invention has low price, small dosage and small pollution coefficient to the environment.
Further, the method comprises the steps of,
the preset time of the oxidation reaction is 2-10 hours; and/or
The heating temperature is 50-80 ℃. According to the scheme, the reaction time for preparing the lithium removal additive is short, the efficiency is high, the lithium removal degree of the product is high, and the requirements of low cost and high quality are met.
Further, the morphology of the ternary positive electrode material includes spherical and/or irregular shapes.
Further, the ternary positive electrode material comprises LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 And LiNi 0.6 Co 0.2 Mn 0.2 O 2 At least one of them.
Further, the alkaline zinc-manganese dioxide battery is prepared by the following steps:
loading the diaphragm into the housing;
mixing powder, rolling, granulating and sieving according to the formula of the anode material, and then filling the mixture into the shell to obtain the anode of the battery;
injecting the electrolyte into the housing such that the separator is fully wetted;
and injecting negative electrode zinc paste into the shell to obtain the battery negative electrode.
Drawings
The following drawings are included to provide an understanding of the invention and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and their description to explain the principles of the invention.
In the accompanying drawings:
FIG. 1 is an X-ray diffraction pattern of a ternary positive electrode material before delithiation and after delithiation using the preparation method of the present invention;
FIG. 2 is a graph showing the discharge of an alkaline zinc-manganese cell without added delithiated additives and an alkaline zinc-manganese cell with added delithiated additives of the present invention in a 1500/650mW,1.05V discharge mode;
FIG. 3 is a graph showing the discharge of alkaline zinc-manganese cells without added delithiated additives and alkaline zinc-manganese cells with added delithiated additives of the present invention in 1000mA,10s/m,24h/d,0.9V discharge mode;
FIG. 4 is a graph showing the discharge of an alkaline zinc-manganese cell without added delithiated additive and an alkaline zinc-manganese cell with added delithiated additive of the present invention in 250mA,1h/d,0.9V discharge mode; and
fig. 5 is a graph showing discharge curves of an alkaline zinc-manganese cell without added delithiated additives and an alkaline zinc-manganese cell with added delithiated additives of the present invention in 100ma,1h/d,0.9V discharge mode.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the invention may be practiced without one or more of these details. In other instances, well-known features have not been described in detail in order to avoid obscuring the invention.
In the following description, a detailed description will be given for the purpose of thoroughly understanding the present invention. It should be appreciated that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of these exemplary embodiments to those skilled in the art. It will be apparent that embodiments of the invention may be practiced without limitation to the specific details that are familiar to those skilled in the art. Preferred embodiments of the present invention are described in detail below, however, the present invention may have other embodiments in addition to these detailed descriptions.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is intended to include the plural unless the context clearly indicates otherwise. Furthermore, it will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
The invention provides an alkaline zinc-manganese dioxide battery which comprises a shell, a diaphragm arranged in the shell, and a battery positive electrode and a battery negative electrode which are positioned in the shell and separated by the diaphragm. The battery anode is formed by mixing, rolling, granulating, sieving and the like of an anode material and then filling the anode material into the shell. The battery negative electrode includes a negative electrode zinc paste. After the preparation of the positive electrode of the battery is completed, electrolyte is injected into the shell so that the separator is completely wetted, and then negative electrode zinc paste is injected into the shell to form the negative electrode of the battery. The negative electrode zinc paste can be composed of zinc powder, a negative electrode binder and a negative electrode electrolyte.
The formula of the positive electrode material of the battery positive electrode is as follows:
manganese dioxide accounting for 40 to 80 percent of the mass ratio,
a delithiated additive accounting for 10 to 50 percent of the mass ratio,
2 to 5 percent of positive electrode electrolyte,
conductive agent with mass ratio of 3% -7%
And the mass ratio of the adhesive is 0.1-0.4%.
Preferably, the positive electrode material formula of the battery positive electrode is as follows:
manganese dioxide accounting for 60 to 73 percent of the mass ratio,
a delithiated additive accounting for 20 to 30 percent of the mass,
positive electrode electrolyte with the mass ratio of 2.5-3.5%,
conductive agent with mass ratio of 4% -6%
And the mass ratio of the adhesive is 0.3-0.4%.
Wherein the delithiated additive may be an electrochemically active material having a higher oxidation state. More specifically, the delithiated additive may be a ternary positive electrode material having a higher oxidation state. Preferably, the delithiation degree of the delithiation state additive is 0.32 to 0.96. More preferably, the delithiation degree of the delithiation state additive is 0.54 to 0.95.
The alkaline zinc-manganese dioxide battery has good discharge performance and can simultaneously realize high-current discharge and low-current discharge.
Further, the electrolyte and the positive electrode electrolyte are preferably aqueous solutions of alkali metal hydroxides, and may be, for example, aqueous solutions having a mass fraction of 30 to 36%. Preferably, the electrolyte and the positive electrode electrolyte may be 32% KOH aqueous solution. The conductive agent is at least one selected from graphite, semi-expanded graphite, fully expanded graphite and graphene.
The manganese dioxide is preferably electrolytic manganese dioxide, and the purity thereof is preferably 90 to 92%, more preferably 92%. And the content of copper, nickel, iron, mercury and other elements contained in the electrolytic manganese dioxide is less than or equal to 0.02 percent, and the moisture content is less than or equal to 2 percent.
The delithiated state additive can be prepared by a method comprising a reaction step and a post-treatment step.
In the reaction step, the oxidant is first thoroughly mixed with the ternary cathode material in water (preferably deionized water) while heating, preferably at constant temperature, to effect an oxidation reaction for a predetermined duration. Preferably, the heating temperature is 50℃to 80 ℃. Preferably, the preset time for the oxidation reaction is 2 to 10 hours.
When the lithium removal temperature is lower than 50 ℃, the lithium removal degree of the final product is low, namely the lithium removal degree is insufficient, the quality of the obtained lithium removal additive (lithium removal nickel-containing ternary material) is poor, the lithium removal time is long, and the production efficiency is low. When the lithium removal temperature is higher than 80 ℃, the lithium removal reaction is too severe, so that reaction byproducts are increased, and the structure of the lithium removal product is destroyed, which makes it difficult to remove.
When the lithium removal time is less than 2 hours, the final product has low lithium removal degree and poor quality. When the lithium removal time is more than 10 hours, the production efficiency is low. Thus, the quality of the product obtained at the reaction temperatures and reaction times defined in the present application may be significantly better than the quality of the final product obtained under other conditions.
After the oxidation reaction is finished, a post-treatment step can be performed. In the post-treatment step, the obtained oxidation reaction product is sequentially washed, filtered and dried, so that the delithiated additive is obtained. Wherein, the filtration can adopt suction filtration.
More specifically, the oxidizing agent may be at least one selected from sodium hypochlorite, potassium hypochlorite, sodium persulfate, and potassium persulfate. That is, the oxidizing agent may be a single one of the above substances or may be a combination of two or more of the above substances.
Among them, the oxidizing agent is preferably prepared as a solution, for example, an aqueous solution having a mass concentration of 0.05g/mL to 0.25 g/mL. The mass concentration of the oxidizing agent is preferably 0.1g/mL to 0.25g/mL, more preferably 0.1g/mL to 0.2g/mL.
If the initial concentration of the oxidizing agent is too low, the reaction may be incomplete during the delithiation process, eventually leading to a low delithiation of the product. If the initial concentration of the oxidant is too high, the reaction cost is high, and the product needs to be cleaned for more times after the reaction, so that the production efficiency is low. Therefore, the alkaline solution with the concentration range is selected to ensure that the reaction is complete, a product with higher lithium removal degree is obtained, the reaction cost is reduced, and the production efficiency is improved. In addition, the oxidant can be dissolved in water, so that the dissolution heat can be alleviated, and the reaction risk can be reduced.
In addition, the mass ratio of the oxidizing agent to the ternary positive electrode material is preferably 1:3 to 4:1. More preferably 2:3 to 2:1. When the mass ratio of the oxidant to the ternary cathode material is lower than 2:3, the reaction conversion rate is low. When the mass ratio of the oxidant to the ternary positive electrode material is higher than 2:1, the structure of the ternary positive electrode material is destroyed, resulting in low yield. And too much oxidant can cause the wasting of resources, and the cleaning efficiency is lower, is unfavorable for mass production.
The ternary positive electrode material can be LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 And LiNi 0.6 Co 0.2 Mn 0.2 O 2 At least one of them. That is, the ternary positive electrode material may be one or a combination of a plurality of 523 system ternary materials, 111 system ternary materials, 811 system ternary materials or 622 system ternary materials.
Further, the morphology of the ternary positive electrode material may include spherical and/or irregular shapes. For example, the ternary positive electrode material may be formed as a powder of spherical particles and/or a powder of irregular particles.
The preparation method has the technical effects of simple and convenient operation, easy control, low equipment requirement, easy realization of mass production cost, short consumption time, low pollution, no pollution and high product yield. The delithiation degree of the obtained delithiation state additive can reach 0.17 or more, for example, can be between 0.17 and 0.99. Preferably between 0.32 and 0.96, more preferably between 0.54 and 0.95.
The preparation method of the present invention will be described in more detail with reference to specific examples.
Example 1
The sodium persulfate solution with the concentration of 0.05g/mL and the ternary positive electrode material are fully mixed in water according to the mass ratio of 2:1, heated to 80 ℃ and reacted for 4 hours. And (3) cleaning, filtering and drying the obtained oxidation reaction product to obtain the delithiated additive. The delithiation degree of the delithiated additive is determined.
The battery positive electrode was prepared from 71.7% of electrolytic manganese dioxide, 5% of a conductive agent, 3% of a positive electrode electrolyte, 0.3% of a binder, and 20% of the above delithiated additive, and assembled into a battery.
Wherein the purity of the electrolytic manganese dioxide is 92%. The conductive agent consists of semi-expanded graphite and fully-expanded graphite in a mass ratio of 1:1. The positive electrode electrolyte was a 32% aqueous alkali metal hydroxide solution.
The discharge performance of the battery was measured.
Example 2
The oxidant adopts 0.1g/mL sodium persulfate solution, and the rest materials have the same composition and preparation method as in example 1.
Example 3
The oxidant adopts 0.15g/mL sodium persulfate solution, and the rest materials have the same composition and preparation method as in example 1.
Example 4
The oxidant adopts 0.2g/mL sodium persulfate solution, and the rest materials have the same composition and preparation method as in example 1.
Example 5
The oxidant adopts 0.25g/mL sodium persulfate solution, and the rest materials have the same composition and preparation method as in example 1.
Comparative example 1
The oxidant adopts 0.03g/mL sodium persulfate solution, and the rest materials have the same composition and preparation method as in example 1.
Comparative example 2
The oxidant adopts 0.3g/mL sodium persulfate solution, and the rest materials have the same composition and preparation method as in example 1.
The delithiation degree controls of the delithiated additives of examples 1 to 5 and comparative examples 1 to 2, and the corresponding battery discharge performance controls are shown in Table 1.
TABLE 1
Example 6
The oxidant adopts 0.15g/mL sodium persulfate solution, the mass ratio of the oxidant to the ternary cathode material is 1:1, and the composition of the rest materials is the same as that of the preparation method of the example 1.
Example 7
The mass ratio of the oxidant to the ternary cathode material is 1:2, and the composition and preparation method of the rest substances are the same as those of the example 6.
Example 8
The mass ratio of the oxidant to the ternary cathode material is 1:3, and the composition and preparation method of the rest substances are the same as those of the example 6.
Example 9
The mass ratio of the oxidant to the ternary cathode material is 2:3, and the composition and preparation method of the rest substances are the same as those of the example 6.
Comparative example 3
The mass ratio of the oxidant to the ternary cathode material is 3:1, and the composition and preparation method of the rest substances are the same as those of the example 6.
Comparative example 4
The mass ratio of the oxidant to the ternary cathode material is 4:1, and the composition and preparation method of the rest substances are the same as those of the example 6.
The delithiation degree controls of the delithiated additives of examples 3, 6 to 9, and comparative examples 3, 4, and the corresponding battery discharge performance controls are shown in Table 2.
TABLE 2
Example 10
The oxidant adopts 0.15g/mL sodium persulfate solution, the mass ratio of the oxidant to the ternary cathode material is 2:1, the reaction temperature is 50 ℃, and the composition of the rest materials is the same as that of the preparation method of the example 1.
Example 11
The reaction temperature was 60℃and the composition of the remaining materials was the same as in example 10.
Comparative example 5
The reaction temperature was 90℃and the composition of the remaining materials was the same as in example 10.
Comparative example 6
The reaction temperature was 40℃and the composition of the remaining materials was the same as in example 10.
The delithiation degree controls of the delithiated additives of examples 3, 10, 11 and comparative examples 5, 6, and the corresponding battery discharge performance controls are shown in table 3.
TABLE 3 Table 3
Example 12
The oxidant adopts 0.15g/mL sodium persulfate solution, the mass ratio of the oxidant to the ternary cathode material is 2:1, the lithium removal reaction temperature is 80 ℃, the reaction time is 2 hours, and the composition of the rest materials is the same as that of the preparation method in example 1.
Example 13
The reaction time was 6h, and the composition of the remaining materials was the same as in example 12.
Example 14
The reaction time was 8h, and the composition of the remaining materials was the same as in example 12.
Example 15
The reaction time was 10h, and the composition of the remaining materials was the same as in example 12.
Comparative example 7
The reaction time was 12h, and the composition of the remaining materials was the same as in example 12.
Comparative example 8
The reaction time was 14h, and the composition of the remaining materials was the same as in example 12.
The delithiation degree controls of the delithiated additives of examples 3, 12 to 15 and comparative examples 7 and 8, and the corresponding battery discharge performance controls are shown in Table 4.
TABLE 4 Table 4
Example 16
The oxidant adopts 0.15g/mL potassium persulfate solution, the mass ratio of the oxidant to the ternary cathode material is 2:1, the lithium removal reaction temperature is 80 ℃, the reaction time is 4 hours, the composition of the rest materials is the same as that of the preparation method of the example 1, and the composition of the rest materials is the same as that of the preparation method of the example 1.
Example 17
The oxidant was a sodium hypochlorite solution of 0.15g/mL, and the remainder had the same composition as in example 16.
Example 18
The oxidant was a 0.15g/mL potassium hypochlorite solution, and the rest of the composition and preparation were the same as in example 16.
The delithiation controls for the delithiated additives of examples 3, 16-18, and the corresponding battery discharge performance controls are shown in Table 5.
TABLE 5
Example 19
The oxidant adopts 0.15g/mL sodium persulfate solution, the mass ratio of the oxidant to the ternary positive electrode material is 2:1, the lithium removal reaction temperature is 80 ℃, and the reaction time is 4 hours, so as to prepare the lithium removal additive.
81.7% of electrolytic manganese dioxide, 5% of conductive agent, 3% of positive electrode electrolyte, 0.3% of binder and 10% of the delithiated additive are prepared into a battery positive electrode, and the battery is assembled.
The rest of the composition and preparation method are the same as in example 1.
Example 20
The formula of the positive electrode material is as follows: 61.6% electrolytic manganese dioxide, 5% conductive agent, 3% positive electrode electrolyte, 0.4% binder, and 30% delithiated additive of example 19 above.
The rest of the composition and preparation method are the same as in example 19.
Example 21
The formula of the positive electrode material is as follows: 51.6% electrolytic manganese dioxide, 5% conductive agent, 3% positive electrode electrolyte, 0.4% binder, and 40% delithiated additive of example 19 above.
The rest of the composition and preparation method are the same as in example 19.
Example 22
The formula of the positive electrode material is as follows: 41.6% electrolytic manganese dioxide, 5% conductive agent, 3% positive electrode electrolyte, 0.4% binder, and 50% delithiated additive of example 19 above.
The rest of the composition and preparation method are the same as in example 19.
Comparative example 9
The formula of the positive electrode material is as follows: 91.6% of electrolytic manganese dioxide, 5% of conductive agent, 3% of positive electrode electrolyte and 0.4% of binder, and does not contain delithiated additives.
The rest of the composition and preparation method are the same as in example 19.
The delithiation degree controls of the delithiated additives of examples 3, 19 to 22, and comparative example 9, and the corresponding battery discharge performance controls are shown in Table 6.
TABLE 6
XRD (X-ray diffraction) test was performed on the ternary material before preparation and the delithiated additive obtained by the reaction, and the result is referred to FIG. 1. The four spectral lines are sequentially provided with a ternary material without lithium removal, a ternary material with lithium removal degree of 0.44, a ternary material with lithium removal degree of 0.96 and a ternary material with lithium removal degree of 0.99 from bottom to top.
When the delithiation degree is not more than 0.96, no change is found in the peak shape of the diffraction peak, and only the intensity is reduced, which indicates that the ternary material structure is not destroyed. However, the spectral line position after delithiation is slightly shifted to the left compared to the ternary material without delithiation, because the lattice spacing becomes larger due to the contraction of the unit cell caused by the elution of lithium in the ternary material. However, when the delithiation degree is more than 0.96, a new peak appears in the spectrogram, because the delithiation degree is too high, the material structure is destroyed, and new substances are generated.
The electrical properties of the alkaline zinc-manganese dioxide cell of the present invention will be described in detail with reference to fig. 2, 3, 4 and 5.
Among them, fig. 2 is a discharge contrast curve of an alkaline zinc-manganese battery using only EMD (electrolytic manganese dioxide ) as an active material, and a battery using both EMD and delithiated additives. The discharge mode is: 1500/650mW,1.05V.
Fig. 3 is a discharge contrast curve for alkaline zinc-manganese cells employing only EMD, and cells incorporating both EMD and delithiated additives. The discharge mode is: 1000mA,10s/m,24h/d,0.9V.
Fig. 4 is a discharge contrast curve for alkaline zinc-manganese cells employing only EMD, and cells incorporating both EMD and delithiated additives. The discharge mode is: 250mA 1h/d 0.9V.
Fig. 5 is a discharge contrast curve for alkaline zinc-manganese cells employing only EMD, and cells incorporating both EMD and delithiated additives. The discharge mode is: 100mA 1h/d 0.9V.
Among them, an alkaline zinc-manganese battery using only EMD was comparative example 9, and a battery in which EMD and delithiated additives were mixed was example 3.
It can be seen from the graph that after the lithium removal material is added, the open-circuit voltage and the voltage platform of the battery are both raised, that is, the high-current discharge performance, the medium-current discharge performance and the low-current discharge performance of the battery are all improved.
The processes, steps described in all the preferred embodiments described above are examples only. Unless adverse effects occur, various processing operations may be performed in an order different from that of the above-described flow. The step sequence of the above-mentioned flow can also be added, combined or deleted according to the actual requirement.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing particular implementations only and is not intended to be limiting of the invention. Features described herein in one embodiment may be applied to another embodiment alone or in combination with other features unless the features are not applicable or otherwise indicated in the other embodiment.
The present invention has been illustrated by the above-described embodiments, but it should be understood that the above-described embodiments are for purposes of illustration and description only and are not intended to limit the invention to the embodiments described. In addition, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications are possible in light of the teachings of the invention, which variations and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. An alkaline zinc-manganese battery is characterized by comprising a shell, wherein a battery anode and a battery cathode are arranged in the shell and are separated by a diaphragm, electrolyte is filled in the shell,
the formula of the positive electrode material of the battery positive electrode is as follows:
manganese dioxide with the mass ratio of 40-80%,
the weight ratio of the delithiated additive is 10-50%, the delithiation degree of the delithiated additive is 0.92-0.96,
the mass ratio of the positive electrolyte is 2-5%,
the mass ratio of the conductive agent is 3-7%,
an adhesive, wherein the mass ratio of the adhesive is 0.1-0.4%;
the delithiated state additive is prepared by the following steps:
a reaction step of fully mixing an oxidant and a ternary positive electrode material in water and heating the mixture to perform an oxidation reaction for a preset time,
and a post-treatment step, namely cleaning, filtering and drying the obtained oxidation reaction product to obtain the delithiated additive.
2. The alkaline zinc-manganese dioxide cell of claim 1, wherein the positive electrode material is formulated as:
manganese dioxide with the mass ratio of 60-73%,
the lithium-removing additive accounts for 20 to 30 percent of the mass,
the mass ratio of the positive electrolyte is 2.5-3.5%,
the conductive agent accounts for 4 to 6 percent of the mass,
the mass ratio of the adhesive is 0.3-0.4%.
3. The alkaline zinc-manganese dioxide cell of claim 1,
the electrolyte and the positive electrode electrolyte are aqueous solutions of alkali metal hydroxide with mass fraction of 30-36%; and/or
The conductive agent is at least one of graphite, semi-expanded graphite, fully-expanded graphite and graphene.
4. The alkaline zinc-manganese dioxide cell of claim 1, wherein the mass ratio of the oxidant to the ternary cathode material is 1:3 to 4:1.
5. The alkaline zinc-manganese dioxide cell according to claim 1, wherein the oxidizing agent is at least one selected from the group consisting of sodium hypochlorite, potassium hypochlorite, sodium persulfate and potassium persulfate, and the oxidizing agent is an aqueous solution having a mass concentration of 0.05g/mL to 0.25 g/mL.
6. The alkaline zinc-manganese dioxide cell of claim 1,
the preset time of the oxidation reaction is 2-10 hours; and/or
The heating temperature is 50-80 ℃.
7. The alkaline zinc-manganese dioxide cell of claim 1, wherein the morphology of the ternary positive electrode material comprises spherical and/or irregular shapes.
8. The alkaline zinc-manganese dioxide cell according to claim 1,characterized in that the ternary positive electrode material comprises LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 And LiNi 0.6 Co 0.2 Mn 0.2 O 2 At least one of them.
9. The alkaline zinc-manganese dioxide cell of any one of claims 1 to 8, which is made by the steps of:
loading the diaphragm into the housing;
mixing powder, rolling, granulating and sieving according to the formula of the anode material, and then filling the mixture into the shell to obtain the anode of the battery;
injecting the electrolyte into the housing such that the separator is fully wetted;
and injecting negative electrode zinc paste into the shell to obtain the battery negative electrode.
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